JPH04211452A - Polyamide molding material with improved processability - Google Patents

Abstract

PURPOSE: To provide a polyamide molding material consisting of a specified ratio of a polyamide, a specified amide, etc., and an additive, and with excellent fluidity, processability and mold releasability, and being useful for molded articles, composite materials, etc.

CONSTITUTION: In a polyamide molding materials with good fluidity, the aimed molding material contains 85-99.9 (wt.)% polyamide such as nylon 66 (A), 0.1-15%, pref. 1-5% amide and/or urea (B) of formulas I-IV [wherein R¹ is at least a 5C (aryl) aliph. hydrocarbon; R² is H, a group of formula V or VI; R³ and R⁴ are each a 2-20C divalent hydrocarbon; m is 1-50; and n is an integer of at least 500 for average mol.wt.] and arbitrarily at most 200% to the sum of ingredients A and B additive (C) being a reinforcing agent such as inorg. fillers and glass fibers.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

The present invention relates to a polyamide molding material with improved processability, a method for producing the same, its use in the production of molded products, sheet products, fibers and composite materials, and molded products, sheet products, fibers and composite materials manufactured from this molding material. Regarding semi-finished products, composite materials and other products. The invention is characterized by the use of small amounts of specific amides and/or ureas which impart significantly improved flow properties to the molding composition.

[0002] Processing of thermoplastic resin by injection molding includes:
Sufficiently low melt viscosity and good mold release properties, and in the case of partially crystalline thermoplastic resins, control of the crystallization rate are most important. If the melt viscosity is too high, it is very difficult or even impossible to obtain an accurate reproduction of the mold. If the mold release properties are poor, the molded product may stick to the mold or become distorted during the process of being removed from the mold. Uncontrolled crystallization can, for example, begin before the mold is completely filled, resulting in a loss of surface quality and mechanical properties of the final product. Therefore, in processing thermoplastic resins, it is very important to be able to control melt viscosity, mold release properties, and crystallization, which affect processability.

Polyamides (PA) have long been found to be satisfactory for many practical applications, can be produced by various methods, can be synthesized from a wide range of different polyamide-forming units, and for special applications can be Types of polymers that can be finished alone or in combination with processing aids, polymer alloy components and inorganic reinforcements (e.g. fillers or glass fibers) to produce materials with special combinations of properties. − is. Polyamides are thus used in large quantities in the production of fibers, plastic moldings and sheet products, and are also used, for example, as hotmelt adhesives and as auxiliaries in many technological applications.

[0004] Conventional types of injection molding materials, which are generally unreinforced, flow quite easily, but in reinforced materials and/or alloys the flowability is greatly reduced. This is a particularly serious disadvantage since reinforced polyamides and polyamide alloys have particularly advantageous mechanical properties. This reduced flowability limits the use of polyamide molding materials. Therefore, it is desired to overcome this drawback.

Mold release agents for polyamides are known;
For example silicone oil, stearic acid and its calcium or zinc salts (Kunststoffe 47, 389
(1957)), long chain aliphatic esters (DAS 1
081 218), aliphatic alcohols (Kunstst
off-Handbuch Volume VI, Polyamide
e, published by Carl Hanser Verlag,
Munich 1966). All of these exhibit drawbacks, such as insufficient efficacy or severe incompatibility when used in large quantities, or a reduction in molecular weight or difficulty in incorporation into the material (liquid addition). Was.

[0006]Therefore, there is a need for polyamide molding materials with very good fluidity.

It has now been found that polyamide molding materials containing small amounts of certain amides and/or ureas have greatly improved flow properties without any of the above-mentioned disadvantages. Therefore, the present invention provides a novel polyamide molding material with good fluidity, comprising: A) 85-99.9% by weight of a polyamide known per se;
) General formula (I)-(IV)

[0008]

[Chemical formula 3]

[0009] Here, R1 are independently of each other an (aryl)aliphatic hydrocarbon having at least 5, preferably at least 10 carbon atoms, and R2 are independently of each other hydrogen or a group of formula (V) and (VI)

0010

[C4]

A group corresponding to R
3 and R4 are, independently of each other, divalent carbon atoms having 2 to 10 carbon atoms, which may contain heteroatoms, and which can be linear or branched, open chain or cyclic, aliphatic or aromatic. Hydrogen, preferably an alkylene group having 2-6 carbon atoms, especially R
In the case of 3, C2H4 and in the case of R4, C4H8 is preferred, m is an integer with a value of 1-50, preferably 1-10, most preferably 3-10, and n is a formula (II) and ( The average molecular weight (Mn) of the polyamidoamine on which the compound IV) is based is at least 500, preferably at least 1000, and 50,000 g/mol-1
an integer chosen such that the additives corresponding to formulas (II) and (IV) can have any terminal group (e.g. amine or carboxyl); or 0.1-15% by weight of urea, and optionally C) 200% by weight relative to the sum of A) and B)
The present invention relates to polyamide molding materials, characterized in that they contain the customary additives up to.

The invention also relates to a method for producing the new polyamide molding material and its use in the production of molded articles, sheet products, fibers, semi-finished products, composite materials and other products.

Additives B) of the formulas (I)-(IV) are of the general formula (VII)

[0014]

[C5]

A polyamine corresponding to the general formula (VI
II)

[0016]

[C6]

It is derived from a polyamidoamine corresponding to ##STR2##

The additives can be prepared by reaction of polyamines (VII) or polyamidoamines (VIII) with carboxylic acids or derivatives thereof or with urea-forming compounds, preferably isocyanates, in solution or without solvent. can.

These are essentially known or can be produced by known methods. The following formula (I)-(IV
) is a specific example of a compound:

[0020]

[C7]

[0021]

[Chemical formula 8]

[0022]

[Chemical formula 9]

Additives B) of the formulas (I) to (IV) can be prepared in principle by any method known to the person skilled in the art for the preparation of amides or ureas.

Additives of formula (I) and (II) are of formula (V
Preference is given to preparing them from the corresponding polyamines of II) or (VIII) by solvent-free amidation using carboxylic acids and optionally customary catalysts. Approximately 1 depending on each additive
Temperatures of 60°C to about 280°C are suitable. The additives of formulas (I) and (II) may contain a part of their acid, preferably up to 50 mol %, in particular up to 25 mol %, in the form of a salt of a polyamine with an acid instead of an amide. . Mixtures of acids can also be used. Carboxylic acids or carboxylic acid derivatives having up to 6 carbon atoms, such as acetic acid, can also be used in part, but the carboxylic acid residue R1 must predominate.

For example, in the case of compound (I), one acid is used, for example, to amidate the primary amino group, and then the next acid is used to amidate the secondary amino group.

The following are examples of acids suitable for deriving the group R1: lauric acid, myristic acid, hexadecanoic acid (
palmitic acid), octadecanoic acid (stearic acid) and docosanoic acid (behenic acid). These are also the preferred acids.

Diethylene triamine and its higher homologs, dipropylene triamine and bis-hexamethylene triamine are preferred polyamines (VII
). Additives of formulas (I) and (II) can also be prepared by reaction of compounds of formulas (VII) and (VIII) with carboxylic acids or suitable derivatives thereof, such as acid chlorides, in solution. Methods for carrying out this reaction are known.

The additives of formulas (I) and (II) can contain a small excess of carboxylic acid and/or amine groups. Furthermore, the additives of formulas (I) and (II) can also contain a proportion (≦20%) of tertiary amino groups or rings derived from polyamines (VII).

Compounds of formula (III) and (IV) are prepared from compounds of formula (VII) and (VIII) by reaction with a urea-forming reactant, preferably an isocyanate. The isocyanate used may correspond to the acid R1-COOH. Preferably, the reaction is carried out in solution. Methods for this reaction are known.

The polyamide amines of formula (VIII) can contain, in addition to dicarboxylic acids and triamines, other polyamide-forming units, preferably caprolactam. Triamines can be partially or completely replaced by higher polyamines. Compounds of formula (VIII) are preferably prepared from adipic acid and diethylene triamine and optionally with the addition of caprolactam.

Examples of the preparation of additives used according to the invention can be found in the Examples section. Further details regarding the manufacture of the additives can be found in our own previously unpublished application P 3 921 259.9 (LeA
26 941).

The finished molding material contains this additive at a concentration of 0.1-1
5% by weight, preferably 0.5-8% by weight, most preferably 1-5% by weight.

The materials used according to the invention are known as such or can be produced by known methods. These can be used alone or in any mixture.

In addition to the compounds of the formulas (I) to (IV), the polyamide molding material may contain additives as defined under C), such as fillers and/or reinforcing materials (glass fibers, glass beads, aramid fibers, carbon fibers, inorganic fillers, etc.), plasticizers, flowability improving aids, UV stabilizers, antioxidants, pigments, dyes, mold release agents, anti-softening agents, additives that reduce water absorption (preferably monophenol- nucleating agents, crystallization promoters or inhibitors, and polymer alloy components (e.g. impact modifiers known from the literature). ) can be included. These can be used alone or as concentrates.

Further suitable flow-improving aids are described in our own unpublished patent application P 3 914 0
48.2 (LeA 26 824).

The following are examples of suitable polymer alloy components: diene rubbers, acrylate rubbers, polyethylene, polypropylene, ethylene/propylene copolymers, ethylene/ 1-butene copolymer, ethylene/propylene/diene terpolymer, ethylene/acrylic acid/acrylic acid ester terpolymer, ethylene/vinyl acetate copolymer, polyoctenylene, polystyrene, (α-methyl)-styrene/
(meth)acrylonitrile copolymer, (meth)acrylonitrile/butadiene/(α-methyl)styrene polymer (ABS), high-impact polystyrene, polycarbonate, aromatic polyester (carbonate),
Polyesters such as polyethylene terephthalate, polysulfones, polyphenylene oxides, polyether ketones, polyether ether ketones, polyamide amides, polyether sulfones, polyether imides, polyester imides and polyimides. If necessary, the polymer alloy must be chemically modified, at least in part, so that partial coupling of the two phases occurs. This can be done, for example, by copolymers of ethylene and/or propylene with small amounts of acrylic acid, or ethylene/propylene (diene) polymers grafted with small amounts of maleic anhydride, or polyphenylene oxides grafted with small amounts of maleic anhydride. Alternatively, it can be carried out by using it as a mixture with an unmodified alloy component. Coupling can also occur via ester or epoxide groups. Additionally, coupling can be effected, for example, by the presence of suitable low molecular weight or polymeric reagents that provide compatibility;
For example, an acrylonitrile/styrene/acrylic acid terpolymer can be used as a compatibility agent in alloys containing ABS. The alloy component can also contain active end groups that react with the polyamide, such as amino-terminated or carboxyl-terminated polydiene rubbers.

Rubber can also be grafted onto the core/sheath structure.

Mixtures of polyamides with other polymers and/or alloy components, such as PA 66, an alloy of polyphenylene oxide and high-impact polystyrene, or an alloy of PA 66, an aromatic polyester and an impact modifier, or a polyamide. 6. (Meth)acrylonitrile/(α-methyl)-styrene copolymers and polybutadiene- or acrylate-graft rubber alloys described in the literature as impact modifiers can be prepared according to the present invention. .

Amorphous polyamides which are compatible and/or incompatible with the polyamides used according to the invention can also be used as additives. For example, PA 6 I (polyhexamethylene isophthalamide) or polyamides of isophthalic acid, terephthalic acid, hexamethylene diamine and optionally 4,4'-diamino dicyclohexyl methane can also be used as amorphous polyamides.

In addition to the polyamides used according to the invention,
In mixtures and/or alloys containing other polymers,
The polyamide used according to the invention (for example PA 66
and copolyamides thereof) should not be less than about 40% by weight, preferably not more than about 50% by weight.

Preferred alloy components are those conventionally used to increase impact resistance at room temperature and/or in a dry state (impact modifiers) and those having a glass transition temperature of at least 9.
It is an amorphous thermoplastic resin having a temperature of 0°C, preferably at least 120°C, most preferably 140°C or higher.

Partially crystalline and amorphous polyamides or mixtures thereof are suitable as polyamide A according to the invention. P
A 6,66,6T/6,610,1212,11,
Preference is given to copolyamides based on 12 and 46 as well as PA 6 and PA 66. PA 6 and
66 and mixtures thereof and copolyamides based on PA 6 and 66 are particularly preferred.

The polyamide molding composition according to the invention is produced by mixing the solvent-free components, preferably in a kneader or extruder. In this case, any method conventionally used for mixing thermoplastics can be used.

The polyamide molding material of the present invention can be finished by injection molding, extrusion molding, pultrusion, molding, film deposition, etc., and can be used to produce molded products, sheet products, fibers, semi-finished products, etc.
Composite materials etc. can be manufactured. These products are also the subject of the present invention.

The polyamide molding materials of the invention have significantly improved flow properties.

Due to the high molecular weight of the additive B) used according to the invention, the polyamide molding compositions according to the invention are not volatile. These are generally solids and therefore easy to add. These have therefore become a valuable enrichment of the state of the art.

The following examples employ common starting materials in typical amounts and are intended to be illustrative of the invention and not limiting.

ηrel was determined on a 1% solution in m-cresol at 25°C. Unless otherwise instructed, the part
Cents are percentages by weight.

[0049]

[Example 1] N, N', N''- by solvent-free amidation
Tris-stearoyl-diethylene triamine
Preparation of 3 (for use according to the invention) 154.5 g of diethylene triamine, 1280 g of stearic acid and 0.3 g of triphenyl phosphite under nitrogen
1 hour at 180-220°C, then 4. at 260°C.
Stirred for 5 hours. After cooling, the reaction mixture was recrystallized from toluene. 1165 g of yellow crystals were obtained with a pour point of 103-10
The temperature was 5°C. The basic nitrogen content was 0.11%, and the carboxyl group content was 0.27%.

[0050]

Example 2 Preparation of essentially fully amidated polyamine 7 using stearic acid by solvent-free amidation (for use according to the invention) Polyethylene based on tetraethylene pentamine and pentaethylene hexamine -Polyamine mixture (polyamine B, B
ayer AG product) 25 g, 156 g stearic acid and 0.1 g triphenyl phosphite,
180-220°C (1 hour) as described in Example 1
and 260°C (5 hours). 110 g of light brown crystals with a melting point of 90-101°C after recrystallization from toluene
I got it. The basic nitrogen content was 0.56% and the carboxyl group content was 0.27%.

[0051]

[Example 3-5] and

[Comparative Example 1] The amide according to Example 1 was converted into polyamide 6
Z at various temperatures with the granules (ηrel is about 4.0)
Extruded through an SK 53-twin screw extruder. The extrusion amount was 30 kg h-1.

The improvement in flowability was determined from the extruder energy consumption.

[0053]

[Example 6-9] and

Comparative Example 2 The PA 6 granules used in Examples 3-5 were mixed with triamide 3 prepared in Example 1 and an amide based on triethylene tetramine, stearic acid and a small amount of acetic acid (Persoftal UK, Bayer).
AG product) at 270° C. as described above.

Table 1 shows the energy consumption.

[0055]

[Table 1]

[0056]

[Example 10-13] and

[Comparative Example 3] The same material was made of high molecular weight PA 6 (ηre
l is about 5) and extruded by the method described in connection with Example 6-9 (extrusion amount: 24 kgh-1).

Data regarding energy consumption are shown in Table 2.

[0058]

[Table 2]

[0059]

[Examples 14 and 15] and

Comparative Example 4 Low viscosity PA 6 (ηrel=2.9) was extruded in the manner described in Examples 3-5 together with the materials used in the previous examples.

Table 3 shows data regarding energy consumption.

[0061]

[Table 3]

[0062]

[Example 16-19] and

[Comparative Example 5-7] PA 6 with average viscosity (ηrel=3
．． 5), amide 3 and polyphenolic compound were dry mixed and extruded (260°C) by the method described in Examples 6-9.

Energy consumption data for these samples and for samples without amide 3 are shown in Table 4.

[0064]

[Table 4] 1) Phenol-formaldehyde condensate (phenol:CH2O=1:0.78) As the examples show, the additive used according to the invention is a very effective flow improver. , even very small doses are effective.

Furthermore, as shown in Table 5, these act as crystallization inhibitors. Thereby, the surface of the molded product can be improved.

[0066]

[Table 5] 1) Example TS (°C) ΔHS (I/g
) TK (℃) ΔHK (g/g)──────
──────────────────────────
────── 19 214.0
55.5 163.5 54
．． 7 Comparative Example 6 215.7 55.5
165.2 57.4 Comparative Example 7
220.6 61.3
172.1 61.71) Determined by DSC (heating rate: 20K min-1; cooling rate: 40K
min-1).

[0067]

[Example 20] and

Comparative Example 8 PA 66 (ηrel=3.0) was mixed with glass fiber (30% relative to the formulation) and 2% (based on the formulation) of the amide according to Example 2 (Example 20) or 0
．． 3% (based on the formulation) of polyethylene wax (Hostalub WE 1, Hoechst
AG product) (Comparative Example 8) and (ZSM 5
3).

The mechanical properties and flow length are shown in Table 6.

[0069]

[Table 6]
Example 20
Comparative Example 8 Ash content (%)
28.8
28.3σR (mPa)
179
183εR (%)
3.0
3.17Ez (mPa)
9451
9407σB3.5 (mPa)
257
258σB (mPa)
274
282EB (mPa)
8308
8269aK1) (KJ/m2)
10.7
10.9an1) (KJ/m2)
51.3
53.6-30℃
46.0
46.2HDT A(
°C) 254
253HDT B(℃
) >254
>253 Flow length 2) (cm)
(280℃)
74 58
1) ISO 180; aK: Method 1A; an: Method 1
c2) Measure of liquidity. Higher values indicate better liquidity.

The main features and aspects of the present invention are as follows.

1. In the polyamide molding material with good fluidity, A) 85-99.9% by weight of a polyamide known per se, B
) General formula (I)-(IV)

[0072]

[Chemical formula 8]

Here, R1 independently represents an (aryl) group having at least 5 carbon atoms, preferably at least 10 carbon atoms.
R) is an aliphatic hydrocarbon, and R2 are independently of each other,
Hydrogen or formulas (V) and (VI)

[0074]

[Chemical formula 9]

A residue corresponding to [0075], preferably hydrogen,
R3 and R4 are independently bivalent carbon atoms having 2 to 10 carbon atoms, which may contain heteroatoms, and which can be linear or branched, open chain or cyclic, aliphatic or aromatic. Hydrogen, preferably an alkylene group having 2-6 carbon atoms, particularly preferably C2H4 for R3, and C4H8 for R4, m is an integer with a value of 1-50, preferably 1-10. , n is such that the average molecular weight (Mn) of the polyamidoamine on which the compounds of formulas (II) and (IV) are based is at least 500, preferably at least 1000, and not more than 50,000 g/mol-1. , and the additives corresponding to formulas (II) and (IV) can have any terminal group (e.g. amine or carboxyl). 1-15% by weight, and optionally C) A) and B
Polyamide molding materials, characterized in that they contain up to 200% by weight of customary additives, based on the total of

2. Polyamide molding material according to paragraph 1, characterized in that the compounds corresponding to formulas (I)-(IV) are used in an amount of preferably 0.5-8% by weight, most preferably 1-5% by weight. Polyamide molding material 3.
3. Polyamide molding material according to claims 1 and 2, characterized in that, in particular, compound 1-26 is used as additive B).

4. In the polyamide molding material according to item 1-3, it is preferable to use compounds corresponding to the formulas (I) to (III), in which the group R1 in the formula (I) is preferably an aliphatic compound having at least 12 carbon atoms. groups, especially C1
2H35, C15H31, C17H35, C20H41
, C21H43 and C22H45, either singly or in mixtures, and acids having up to 6 carbon atoms, for example acetic acid, among others, can also be used.

5. Polyamide molding material according to paragraphs 1-4, characterized in that the use of PA 6, PA 66 or mixtures thereof and copolymers based on PA 6 or PA 66 is particularly preferred.

6. In the polyamide molding compositions according to paragraph 1-4, the substances used as additive C) are, in particular, single or in mixtures, reinforcing materials (glass fibers, inorganic fillers, etc.), polymer alloy components (in particular impact-resistant improver)
, other flow improvers, customary lubricants and mold release agents, pigments and dyes, UV stabilizers, antioxidants, phenolic compounds (especially bis-phenols and (alkyl) ) A polyamide molding material characterized in that it is a phenol-formaldehyde condensate) and a flame retardant.

7. In a method for producing a polyamide molding material with good fluidity, which is produced by adding a fluidity improver to a high molecular weight polyamide, in one or more steps that do not contain a solvent A)
B) 85-99.9% by weight of high molecular weight polyamide
0.1-15% of amides of the general formulas (I)-(IV) and/or urea as described in Section 1 and optionally up to 200% by weight of conventional additives C, based on the sum of A) and B). ).

8. Production of molded articles, sheet products, fibers, semi-finished products, composite materials and finishing from injection molding, extrusion molding, pultrusion, film deposition or melting of the polyamide molding materials with good flowability as described in paragraphs 1-6. Use in the manufacture of other products by other methods known as methods.

9. Molded articles, sheet products, fibers, semi-finished products, composite materials and other products of the polyamide molding materials according to paragraphs 1-6.

Claims (3)

[Claims] Claim 1: A polyamide molding material with good fluidity, comprising: A) 85-99.9% by weight of a previously known polyamide; B) a general formula (I)-(IV) [Formula 1] where R1 is , independently of each other, the number of carbon atoms is at least 5
, preferably at least 10 (aryl)aliphatic hydrocarbons, R2 are independently of each other hydrogen or of the formula (V
) and (VI) are residues corresponding to [Formula 2], preferably hydrogen, and R3 and R4
are, independently of each other, divalent hydrocarbons having 2-10 carbon atoms, which may contain heteroatoms, and which may be linear or branched, open-chain or cyclic, aliphatic or aromatic. , an alkylene group having 2-6 carbon atoms is preferred, in particular C2H4 for R3 and C4H8 for R4, m is an integer with a value of 1-50, preferably 1-10, n
The polyamidoamine on which the compounds of formulas (II) and (IV) are based has an average molecular weight (Mn) of at least 50
0, preferably at least 1000, and 50,00
an integer chosen not to be greater than or equal to 0 g/mol-1, and the additives corresponding to formulas (II) and (IV) can also have any terminal group (e.g. amine or carboxyl). and/or urea 0.1-15
% by weight, and optionally C) 2 relative to the sum of A) and B)
Polyamide molding material characterized in that it contains up to 00% by weight of conventional additives. 2. A polyamide molding material according to claim 1, in which compound 1-26 is used in particular as additive B). Claim 3: In a method for producing a polyamide molding material with good fluidity, which is produced by adding a fluidity improver to a high molecular weight polyamide, in one or more solvent-free stages, A) 85-9
9.9% by weight of the high molecular weight polyamide and B) the amide and/or urea of general formula (I)-(IV) according to claim 1.
．． 1-15% and optionally up to 200% by weight, based on the sum of A) and B), of customary additives C).